CN106384708A - Method for increasing doping concentration of phosphor in nanometer silicon material through employing boron-phosphor codoping - Google Patents

Method for increasing doping concentration of phosphor in nanometer silicon material through employing boron-phosphor codoping Download PDF

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CN106384708A
CN106384708A CN201610835042.6A CN201610835042A CN106384708A CN 106384708 A CN106384708 A CN 106384708A CN 201610835042 A CN201610835042 A CN 201610835042A CN 106384708 A CN106384708 A CN 106384708A
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silicon
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multilayer film
doping
phosphorus
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徐骏
李东珂
陆鹏
李伟
翟颖颖
陈坤基
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Nanjing University
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Abstract

The invention discloses a method for increasing the doping concentration of phosphor in a nanometer silicon material through employing the boron-phosphor codoping technology, and the method comprises the following steps: 1), preparing a multilayer film material doped with nanometer silicon/silicon oxide through employing PECVD; 2), obtaining the multilayer film material doped with nanometer silicon/silicon oxide (a-Si/SiO2) through the alternate conducting of two processes: noncrystalline silicon layer deposition/in-situ oxidation, and obtaining the thickness of the a-Si/SiO2 multilayer film through controlling the time of the noncrystalline silicon layer deposition/in-situ oxidation; 3), carrying out the dehydrogenation processing of the prepared a-Si/SiO2 multilayer film; 4), carrying out the high-temperature annealing under the nitrogen condition after dehydrogenation, enabling polycrystalline silicon to be crystalized to form nanometer silicon, activating foreign matter atoms to enter the nanometer silicon, and achieving the doping of the nanometer silicon. The method prepares the codoping nanometer silicon/silicon oxide multilayer film.

Description

The method being co-doped with improving the phosphorus doping density in nano silicon material using boron phosphorus
First, technical field
The present invention proposes one kind and can solve nano material doping difficulty, improves impurity doping content in nano-silicon Method, especially can be by boron phosphorus and is co-doped with technology to improve the new technique of the Effective Doping concentration of phosphorus in nano silicon-based thin film.
2nd, background technology
Silicon (Si) is a kind of currently the most important semi-conducting material.From the sixties in 20th century, silicon materials are extensively applied In fields such as microelectronics, photovoltaic, semiconductor integrated circuit, the development of the semi-conductor industry based on silicon materials is very big Promote the development of electronics science and information technology.With the development of semiconductor technology and device, it is applied to the silicon material of device The size of material also constantly reduces, and has been enter into deep-submicron or even nanoscale so far, thus the preparation to nano silicon material and thing The research of rationality energy just becomes a current very noticeable field.For nano silicon material, due to quantum size effect Should, the impact of surface and interface effect etc., it presents the characteristics different from body silicon materials, also therefore can develop many New nano-electron based on nano silicon material and optoelectronics device.Excellent photoelectric properties that particularly nano-silicon has, no Toxicity and with existing bulk silicon technology preferably compatibility so that it is at present in photovoltaic, light emitting diode, photodetection The popular domains such as device, bio-imaging have good application prospect.
For semi-conducting material, effectively can be adulterated key and the base being to realize high performance device to material Plinth.Electronic structure and conduction type and conductive capability etc. of semi-conducting material can be regulated and controled by doping, and realize the devices such as pn-junction Part basic structure.Mix phosphorus (P) for example in body silicon materials, it is possible to obtain n-type semiconductor silicon materials；And mix boron (B), permissible Obtain p-type semiconductor silicon materials.But and body silicon materials except that, for nano material, the particularly less quantum of size Point material, there is " automatically cleaning " effect in it, that is, nano-silicon, in order to keep internal stress and formation energy minimum, is invariably prone to mix Enter foreign atom therein and be discharged to surface or external, therefore realize the Effective Doping to nano-silicon in an experiment and be always public affairs The difficult problem recognized.At present, in theoretical and experimental research worker all to various doped chemicals, particularly conventional phosphorus and boron impurity, Doping behavior in nano-silicon launches research.But existing research shows, due to quantum size effect, quantum confined effect and Skin effect makes the doping behavior of nano-silicon become more complicated, and related impuritieses are difficult to be incorporated into inside nano-silicon, such as most of Phosphorus impurity atoms occupy on nanometer silicon face, and the defect state (dangling bonds) that is, nanometer silicon face exists also can be captured most Impurity phosphorus atoms, so that Effective Doping concentration in nano-silicon for the phosphorus reduces further, lead to doping efficiency relatively low accordingly. Therefore how to improve Effective Doping concentration in nano-silicon for the impurity, experimentally realize Nano semiconductor truly Doping is nano silicon material key point practical further.
The present invention proposes a kind of new method improving phosphorus doping density efficiency in nano silicon-based thin film, and that is, boron phosphorus is co-doped with skill Art.Find that impurity boron atom is more likely to occupy the characteristic of nano-silicon surface state in realization based on us, prepared by design The nano silica-base material that boron phosphorus is co-doped with, is co-doped with system using boron phosphorus, boron atom be more likely to occupy the characteristic of surface state so that Boron occupies the surface of nano-silicon, and the dangling bonds of passivated surface first.And phosphorus atoms then more can enter inside nano-silicon, make Obtain Effective Doping concentration to improve, corresponding conductive capability strengthens.Meanwhile, we experimentally pass through capacity plate antenna type radio frequency induction Coupled plasma strengthens chemical vapour deposition technique and is prepared for corresponding material, finds that boron atom can effectively improve really Phosphorus atoms, in the doping content efficiency of nano-silicon, strengthen the electron concentration in nano-silicon.This should for the device of nano silicon material With there being highly important value and significance.
3rd, content of the invention
The present invention seeks to, solve the difficult doping of impurity that in nano silicon material, " automatically cleaning " effect and surface defect state cause And the more low emphasis of doping content and difficulties；Propose to be co-doped with improving the phosphorus doping density in nano silicon material using boron phosphorus Method, improves the Effective Doping concentration of impurity especially in low dimensional semiconductor material, realizes effectively controllable doped, solves such as to receive Impurity Distribution, relative energy-level position etc. in rice silicon materials.
The technical scheme is that, be co-doped with, using boron phosphorus, the side that technology improves the doping content efficiency of phosphorus in nano-silicon Method, that is, in nano-silicon, boron phosphorus is co-doped with improving p-doped doping content is the preparation that boron phosphorus is co-doped with nano silicon-based thin film, and step is as follows：
1) prepare dopen Nano silicon/silicon dioxide multi-layer film material using PECVD；It is passed through during growth dopen Nano silicon thin film Silane (SiH4) amorphous silicon layer deposition is carried out on silicon chip, it is passed through phosphine (PH simultaneously3) and borine (B2H6) be co-doped with realizing boron phosphorus Miscellaneous, and change dopant gas flow to obtain different doping contents (gas nominal concentration)；Growth nano-silicon film material, closes Close silane and impurity gas, be passed through oxygen (O2) carry out in-situ oxidation nano-silicon acquisition silicon dioxide layer；2) pass through alternately Two processes of amorphous silicon layer deposition/in-situ oxidation, are obtained in that doping (impurity is co-doped with) nanometer silicon/silicon dioxide (a-Si/ SiO2) multi-layer film material；Control the when acquisition a-Si/SiO of amorphous silicon layer deposition/in-situ oxidation2The thickness of multilayer film；3) to system Standby a-Si/SiO2Multilayer film carries out Dehydroepiandrosterone derivative；4) to the high temperature anneal carrying out under nitrogen atmosphere after dehydrogenation, make polycrystalline Silicon crystallization forms nano-silicon, and activator impurity atom enters inside nano-silicon, realizes the doping of nano-silicon；Through above step just The nanometer silicon/silicon dioxide multilayer film of codope can be prepared.
Dehydroepiandrosterone derivative refers to multilayer film is carried out with 450 ± 30 DEG C of Dehydroepiandrosterone derivative 0.5-3h,
In pecvd process, rf frequency is kept to be 13.56MHz in CVD whole process, power is 50W, growth temperature is 250±30℃；
After Dehydroepiandrosterone derivative, the high temperature anneal under nitrogen atmosphere 0.5-3 hour is carried out to sample 800-1000 DEG C high Temperature annealing；
Period be passed through diluted in hydrogen to 1%vol phosphine and diluted in hydrogen 1vol% borine to realize boron phosphor codoping, Phosphine is 1 with the volume ratio of borine：0.5～2, change phosphine, borine flow and can obtain different levels of doping (gas is nominally dense Degree) amorphous silicon layer.
In high-temperature annealing process, while non-crystalline silicon is subject to thermal crystallisation to form nano-silicon, foreign atom is also subject to warm-up movement, but In the presence of nano-silicon " automatically cleaning " and skin effect etc., related impuritieses are difficult to be incorporated into inside nano-silicon, and nano-silicon table Planar defect also " can capture " most of phosphorus atoms so that the Effective Doping concentration of phosphorus in nano-silicon reduces, and leads to accordingly relatively low Doping efficiency.The present invention is prepared for, using PECVD and high annealing technology, the nano silicon material that boron phosphorus is co-doped with, using boron atom Remove to occupy the surface of nano-silicon, the dangling bonds of passivated surface, the impact reducing skin effect with " automatically cleaning " is so that foreign matter of phosphor is former Son more enters into inside nano-silicon, and then realizes the raising of phosphorus Effective Doping concentration, and the corresponding electronics participating in conduction The increase of concentration.1. utilize cryotronics spin resonance absorption spectra (ESR) to estimate that the unpaired electron in nano-silicon multilayer film is dense Degree
Using electron spin resonance spectrometer, the multilayer film that different impurities are adulterated accurately is tested under ultralow temperature, obtained Resonance absorption spectral line near the high-intensity magnetic field of Liao Qi center.
In external magnetic field, electronics is acted on by magnetic field:To electron spin upwards with spin downward two kinds The energy difference Δ E=g μ of statebB.If in the microwave providing a fixed frequency perpendicular to the direction of B, in different high-intensity magnetic field B Under, when microwave energy hv meets hv=g μbB, electrons produce Zeeman splitting, transit to upper state from lower state, produce resonance Absorb.According to formula：Hv=g μbB, can be calculated characterization factor g=hv/ μbB.For general material, due to unpaired electron The molecular structure that is located by it of g value and SO coupling act on and being affected, office can be understood by the change of g value The molecular structure information in domain.
In room temperature ESR test, the electronics in nano-silicon is subject to stronger scattering process, and its electron spin resonance absorption is believed Number very faint, and during room temperature noise of instrument can interference detection signal, cause ESR signal to be difficult to be detected, and the letter recording Number easily distortion.But at low temperatures, the scattering that electronics is subject to can substantially weaken, and noise of instrument is less, using low temp. electric Sub- spin resonance technology can more accurately detect the ESR signal of nano-silicon, more accurately analyses in depth nanometer silicon microscopic structure letter Breath.The ESR resonance absorption spectral line that test is obtained carries out (∫ ∫ f (B) dB), its gained function after double integral in magnetic field range The maximum obtaining in the range of B is unpaired electron concentration in nano silicon-based thin film.PECVD and many is adopted in the present invention Prepared by tunic restricted crystallization technology is co-doped with nano silicon material size uniformity, uniform doping, has identical nanometer microcosmic knot Structure, therefore can be accurately obtained the structural information in nano silicon material using cryotronics spin resonance technology.
The mechanism of the present invention is to prepare the nano silicon material that boron phosphorus is co-doped with, and goes to occupy the surface of nano-silicon using boron, passivation The dangling bonds on surface.This can make the impurity phosphorus atoms originally occupying on surface more enter into inside nano-silicon, Jin Ershi The raising of existing phosphorus doping density efficiency, and the corresponding increase participating in conductive electron concentration.Accordingly, experimentally, Wo Menli Strengthen chemical vapour deposition technique with capacity plate antenna type radio frequency induction coupled plasma and be prepared for boron phosphorus with reference to high annealing method The nanometer silicon/silicon dioxide multi-layer film material of codope, tests and the electron concentration comparing under identical phosphorus nominal doping density, Demonstrate the correctness of invention thinking, find that boron phosphorus is co-doped with really improving doping content in nano silicon material for the phosphorus atoms Efficiency, strengthens the electron concentration in nano-silicon effectively.
Beneficial effects of the present invention：
1. a nanometer silicon technology is co-doped with by boron phosphorus, Effective Doping concentration in nano-silicon for the phosphorus can be improved in an experiment, The conduction property of regulation and control nano silicon material.
2. present invention experiment preparation process is simple, has preferable controllability and repeatability.
3. the technological approaches of the present invention and current integrated circuit technology are completely compatible, are conducive to application and the industry of technology Change.
4. the electronic signal in nano-silicon is can accurately measure during characterizing using cryotronics spin resonance technology, can With the more convenient doping situation accurately directly studying impurity in nano-silicon.
4th, brief description
Fig. 1：Boron phosphorus is co-doped with Si NCs/SiO2Multilayer film electron spin resonance absorption spectrum in 2K ultralow temperature.All samples g The factor is all 1.998 conduction band electron signals, and the increase with boron nominal concentration, and its unpaired electron concentration increases, and shows to lead In band, free electron number increases, and the doping content efficiency of phosphorus atoms increases.
Fig. 2：Phosphorus list doping (a) and the Si NCs/SiO of boron phosphor codoping (b)2The FTIR absorption spectra of multilamellar membrane sample.Right Mix sample than phosphorus list, the LSPR of boron phosphor codoping sample absorbs peak-to-peak signal and blue shift occurs, show that in conduction band, free electron number increases Many, the doping content efficiency of phosphorus atoms increases.
5th, specific embodiment
1) prepare the nanometer silicon/silicon dioxide multilayer film of boron phosphor codoping on a silicon substrate；
Using RCA standard cleaning flow process, the p-type monocrystalline substrate (resistivity after cleaning up：1.5-3 Ω cm) and Quartz substrate is positioned in PECVD system and carries out thin film deposition, before growing film first with argon (Ar) to the substrate cleaning up Surface carries out pretreatment, and power is 30W, and reaction pressure is 480mTorr, and the time is 5min, closes argon afterwards, is passed through oxygen, oxygen Change and process 90s.The purpose of pretreatment is the adhesion strengthened between thin film and substrate.In thin film growth process, first it is passed through silane (SiH4) carrying out amorphous silicon layer deposition, silane flow rate is controlled to 5sccm, and the response time is 90s, and period is passed through diluted in hydrogen The 1vol% borine of 1%vol phosphine and diluted in hydrogen, to realize boron phosphor codoping, changes phosphine, borine flow can obtain not The amorphous silicon layer of same doping content (gas nominal concentration).And then, close silane and impurity gas, be passed through the oxygen of 20sccm (O2) carrying out in-situ oxidation acquisition silicon dioxide layer, oxidization time is 90s.Close oxygen afterwards, be passed through silane and doping gas again Body carries out the deposition of amorphous silicon layer, by alternately amorphous silicon deposition and two processes of in-situ oxidation, it is possible to obtain boron phosphorus is altogether Amorphous silicon/silicon dioxide (the a-Si/SiO mixing2) multi-layer film structure.Rf frequency is kept to be 13.56MHz in whole process, work( Rate is 50W, and growth temperature is 250 DEG C. after multilayer film carried out with 450 DEG C of Dehydroepiandrosterone derivative 1h, make the hydrogen of sample interior slow Effusion.After Dehydroepiandrosterone derivative, under nitrogen atmosphere sample is carried out with the high temperature anneal (800-1000 DEG C) of 1 hour, makes amorphous Silicon layer crystallization forms nano-silicon.And in annealing process, can also activate while forming nano-silicon with amorphous crystallization of silicon and mix Hetero atom enters inside nano-silicon, realizes doping.The nanometer silicon/silicon dioxide that codope just can be prepared through above step is many Tunic；
Concrete technology condition is as follows：
RF source frequencies：13.56MHz
RF source power：50W
Underlayer temperature：250℃
SiH4Gas flow：5sccm
PH3Gas flow:Adjustable in 0.3-50sccm
B2H6Gas flow:Adjustable in 0.3-50sccm
Amorphous silicon layer sedimentation time：90s
O2Gas flow：20sccm
Silicon dioxide layer sedimentation time：90s
Multilayer film growth cycle number：70periods
Desorption temperature：450℃
Dehydrogenation atmosphere：N2
Dehydrogenation time：1h
High temperature anneal temperature：800-1000℃
High annealing atmosphere：N2
The high annealing time：1h
2) electron spin resonance absorption spectrum is utilized to calculate the electron concentration in nano-silicon multilayer film；
Using German Bruker company EMX-10/12 type electron spin resonance spectrometer under 2K ultralow temperature to different impurities The multilayer film of doping content is accurately tested, and obtains the resonance absorption spectral line that Liao Qi center high-intensity magnetic field is near 3360G.Meter Calculation obtains SiH4:B2H6:PH3Flow-rate ratio is 5:2:10；5:8:10；5:15:The g-factor of 10 samples is all 1.998, corresponding to certainly Signal by electronics.After its ESR absorption spectra is carried out with ∫ ∫ f (B) dB double integral, obtain unpaired electron concentration difference in sample For 4.66*109, 1.36*1010, 1.82*1010, being co-doped with sample under identical phosphorus nominal concentration, with boron nominal concentration Increase, the concentration of unpaired free electron increases, the doping content efficiency of phosphorus strengthens.
Concrete data see table：
3) surface etc. is utilized to estimate the electron concentration in nano-silicon multilayer film from primitive resonance absorption；
In Si nano-particle, the energy of LSPR can approximate be represented with Drude formula with the relation of electron concentration：
n = ω s p 2 ϵ 0 m e ( ϵ ∞ + 2 ϵ m ) / e 2
Wherein n is free electronic concentration, and e is electron charge, ε0For permittivity of vacuum, meEffective matter for free electron Amount (about 0.3m0), ε∞For the high frequency relative dielectric constant of silicon quantum dot,( For the high frequency relative dielectric constant of body silicon, R is the radius of silicon quantum dot), εmDielectric constant for surrounding medium.
According to the LSPR resonance peak being actually detected, estimate phosphorus list and mixed nano-silicon multilamellar membrane sample (SiH4:B2H6: PH3=5:0:50) electron concentration is 6.1*1019/cm3, the Effective Doping concentration of phosphorus impurities is 0.122%, and doping content is imitated Rate is 1.22%；Boron phosphorus under identical phosphorus nominal concentration is co-doped with nano-silicon multilamellar membrane sample (SiH4:B2H6:PH3=5:5:50) in Electron concentration be 1.14*1020/cm3, the Effective Doping concentration of phosphorus is 0.227%, and the doping content of phosphorus for efficiency is 2.27%.As can be seen here, boron phosphorus is co-doped with the doping content efficiency that technology can effectively improve phosphorus in nano silicon-based thin film.
Concrete data see table：

Claims (5)

1. it is co-doped with, using boron phosphorus, the method that technology improves the doping content efficiency of phosphorus in nano silicon-based thin film, it is characterized in that step such as Under：
1) prepare dopen Nano silicon/silicon dioxide multi-layer film material using PECVD；It is passed through silane during growth dopen Nano silicon thin film (SiH4) amorphous silicon layer deposition is carried out on silicon chip, it is passed through phosphine (PH simultaneously3) and borine (B2H6) to realize boron phosphor codoping, And change dopant gas flow to obtain different doping contents；Growth nano-silicon film material, closes silane and impurity gas, It is passed through oxygen (O2) carry out in-situ oxidation nano-silicon acquisition silicon dioxide layer；2) pass through alternately amorphous silicon layer deposition/in situ Two processes of oxidation, are obtained in that dopen Nano silicon/silicon dioxide (a-Si/SiO2) multi-layer film material；Amorphous silicon layer is controlled to sink The when acquisition a-Si/SiO of long-pending/in-situ oxidation2The thickness of multilayer film；3) a-Si/SiO to preparation2Multilayer film is carried out at dehydrogenation Reason；4) to the high temperature anneal carrying out under nitrogen atmosphere after dehydrogenation, make polysilicon crystal form nano-silicon, and activator impurity is former Son enters inside nano-silicon, realizes the doping of nano-silicon；Nano-silicon/the titanium dioxide of codope just can be prepared through above step Silicon multilayer film.
2. method according to claim 1, is passed through, during it is characterized in that, the 1%vol phosphine that diluted in hydrogen arrives and hydrogen is dilute The 1vol% borine released is 1 to realize boron phosphor codoping, phosphine with the volume ratio of borine：0.5～2, change phosphine, borine flow Obtain the amorphous silicon layer of different levels of doping.
3. method according to claim 1, is characterized in that in pecvd process, and in whole process, holding rf frequency is 13.56MHz, power is 50W, and growth temperature is 250 ± 30 DEG C.
4. method according to claim 1, is characterized in that Dehydroepiandrosterone derivative refers to multilayer film is carried out at 450 ± 30 DEG C of dehydrogenation Reason 0.5-3h.
5. method according to claim 1, after it is characterized in that Dehydroepiandrosterone derivative, the high temperature anneal is under nitrogen atmosphere to sample Product carry out 800-1000 DEG C of the high temperature anneal of 0.5-3 hour.
CN201610835042.6A 2016-09-19 2016-09-19 Method for increasing doping concentration of phosphor in nanometer silicon material through employing boron-phosphor codoping Pending CN106384708A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107204285A (en) * 2017-07-07 2017-09-26 睿力集成电路有限公司 The grid conducting layer of film, its forming method and its formation

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110171773A1 (en) * 2010-01-13 2011-07-14 Atomic Energy Council-Institute Of Nuclear Energy Research Method for Making a Planar Concentrating Solar Cell Assembly with Silicon Quantum Dots
CN102255016A (en) * 2011-08-17 2011-11-23 南京大学 Silicon-based near infrared light emitting material and preparation method
CN103000742A (en) * 2012-12-04 2013-03-27 南京大学 Solar battery with band gap gradual changing silicon quantum dot multilayer film and production method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110171773A1 (en) * 2010-01-13 2011-07-14 Atomic Energy Council-Institute Of Nuclear Energy Research Method for Making a Planar Concentrating Solar Cell Assembly with Silicon Quantum Dots
CN102255016A (en) * 2011-08-17 2011-11-23 南京大学 Silicon-based near infrared light emitting material and preparation method
CN103000742A (en) * 2012-12-04 2013-03-27 南京大学 Solar battery with band gap gradual changing silicon quantum dot multilayer film and production method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107204285A (en) * 2017-07-07 2017-09-26 睿力集成电路有限公司 The grid conducting layer of film, its forming method and its formation
CN107204285B (en) * 2017-07-07 2018-03-30 睿力集成电路有限公司 The grid conducting layer of film, its forming method and its formation

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